TWI636075B - Novel polymer and thermosetting composition containing same - Google Patents

Abstract

The present disclosure relates to a polymer that includes a first repeating unit and at least one end capping group at one end of the polymer. The first repeating unit includes at least one amide imine portion and at least one indane-containing portion. This end cap group can carry out anti-addition ring reaction. The disclosure also relates to a thermosetting composition containing the above polymer.

Description

Novel polymer and thermosetting composition containing the polymer Cross-reference for related applications

This application claims the priority of US Provisional Application Serial No. 61 / 824,529 filed on May 17, 2013, and the contents of this case are hereby incorporated by reference for all.

Uncover areas

The present disclosure relates to a low-temperature curing, highly organic solvent-soluble polyimide polymer and a thermosetting composition containing the polymer. More particularly, this disclosure relates to a thermosetting composition containing the polymer and a multifunctional thiol, for a method for manufacturing a substrate coated with a cured thermosetting film, the film comes from the polymer And multifunctional thiol thermosetting composition. The composition of the present disclosure has a wide range of applications as thermosetting coatings, especially in the electronics industry, for example, as heat-resistant coatings, insulating coatings, dielectric films, barrier coatings, and encapsulants. These coatings can be deposited by various methods, but particularly advantageous are coatings manufactured using inkjet technology.

Expose background

Polyimide is a film-forming resin with excellent electrical, mechanical, chemical and thermal properties that is widely used in the manufacture of electronic components. Every special purpose Has its special physical and chemical requirements. However, in many cases, the polyimide required for this application has limited or no solubility in solvents that are acceptable for coating polyimide films. Due to safety or boiling point issues, several highly polar solvents are unacceptable for membrane casting systems, therefore, soluble systems in medium polar solvents are required. Therefore, many coatings are cast with a slightly more solvent-soluble polyamide film and then cured at high temperature. This will cause some damage to substrates / devices and equipment used in high temperature curing. Furthermore, dehydration of polyamic acid into polyimide shrinks the film by about 15-20%, which often increases the stress on the film and therefore the underlying substrate / device.

The growth of inkjet technology for various coating applications has been excellent. Special advantages include reducing the amount of coating solution required and the ability to coat specific areas, which can reduce the need for photolithography patterning steps. However, in order to reproducibly manufacture semiconductor devices, certain requirements need to be met, such as excellent patterning ability, storage stability, to obtain the minimum number of coatings of the desired film thickness, even if there is a long time between spray use The low delay trend of blocking tiny inkjet nozzles, compatibility with inkjet heads, and uniform droplet formation. The polyamic acid and polyimide of the conventional art are prone to have low solubility in general inkjet solvents, which results in poor drop formation, poor storage stability, and significant clogging of the inkjet nozzles.

Thermosetting compositions of polyimide polymers that are highly soluble in polar solvents used in various applications are needed. This disclosure describes a highly soluble polyimide polymer suitable for microelectronics applications and its novel thermosetting composition. Due to its high solubility, excellent storage stability, and low clogging of inkjet nozzles, the composition of this disclosure Particularly suitable for deposition using inkjet printing.

A brief overview of disclosure

In one aspect, the present disclosure features a polymer that includes a first repeating unit and at least one end capping group at one end of the polymer. The first repeating unit includes at least one polyimide moiety and at least one indane-containing moiety. This end cap group can undergo reverse addition ring-closing reaction (for example, in a solid state at a temperature of up to about 250 ° C).

In another aspect, the present disclosure features a polymer that is a condensation product of: (a) at least one diamine; (b) at least one dianhydride; and (c) at least one monoanhydride, which includes an energy Groups undergoing reverse addition ring-closing reactions (for example, in a solid state at a temperature of up to about 250 ° C). At least one of components (a) and (b) contains an indane-containing portion. The polymer contains at least one end capping group at one end, and this end capping group contains a group capable of undergoing reverse addition ring-closing reaction.

In some embodiments, the above-mentioned polymer may be a polyimide, a polyamic acid, or a copolymer of these.

In some embodiments, the monoanhydride contains a masked maleic anhydride group. For example, this monoanhydride system has the structure (IX): Among them, G series -O-,-(NR ¹⁰⁰ )-,-[C (R ¹⁰¹ ) = C (R ¹⁰² )]-, or-[C = C (R ¹⁰³ ) ₂ ]-, where, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , and R ^{103 are} each independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear or branched, monocyclic or polycyclic alkyl group, or a substituted or Unsubstituted phenyl group, and each of R ¹ , R ² , R ³ and R ⁴ is independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear or branched, monocyclic or Polycyclic alkyl group, a substituted or unsubstituted phenyl group, OR ¹⁰⁴ , CH ₂ OR ¹⁰⁵ , CH ₂ OC (= O) R ¹⁰⁶ , CH ₂ C (= O) OR ¹⁰⁷ , CH ₂ NHR ¹⁰⁸ , CH ₂ NHC (= O) R ¹⁰⁹ , CH ₂ C (= O) N (R ¹¹⁰ ) ₂ , C (= O) OR ¹¹¹ , where R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , Each of R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , and R ¹¹¹ is independently H or a substituted or unsubstituted C ₁ -C ₆ linear, branched, or monocyclic alkyl group.

In some embodiments, the end cap group includes a masked maleimide group. For example, the end cap group may contain a structure (IXa) part: Among them, G series -O-,-(NR ¹⁰⁰ )-,-[C (R ¹⁰¹ ) = C (R ¹⁰² )]-, or-[C = C (R ¹⁰³ ) ₂ ]-, where, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , and R ^{103 are} each independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic or polycyclic alkyl group, or a substituted Or unsubstituted phenyl group, and each of R ¹ , R ² , R ³ and R ⁴ is independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic Or polycyclic alkyl group, a substituted or unsubstituted phenyl group, OR ¹⁰⁴ , CH ₂ OR ¹⁰⁵ , CH ₂ OC (= O) R ¹⁰⁶ , CH ₂ C (= O) OR ¹⁰⁷ , CH ₂ NHR ¹⁰⁸ , CH ₂ NHC (= O) R ¹⁰⁹ , CH ₂ C (= O) N (R ¹¹⁰ ) ₂ , C (= O) OR ¹¹¹ , where R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , and R ^{111 are} each independently H, or a substituted or unsubstituted C ₁ -C ₆ linear, branched, or monocyclic alkyl group.

In certain embodiments, the indane-containing portion includes Wherein, each of R ¹¹ -R ³⁰ is independently H or a substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl group (for example, CH ₃ ).

In some embodiments, the polymer may further include a second repeating unit different from the first repeating unit.

In certain embodiments, the component containing the indane-containing portion is at least about 25 mole% of components (a) and (b).

On the other hand, the present disclosure relates to the capped polyimide polymer of structure I.

Among them, Z is a divalent organic group capable of performing reverse addition ring-closing reaction (for example, in a solid state at a temperature of up to about 250 ° C), n is an integer greater than 5, and X is a group selected from X ¹ and X ² One or more divalent organic groups of the group, wherein X ¹ is one or more of the structures X ^1a -X ^1d , wherein R ¹¹ to R ^{21 are} independently H, substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl groups (for example, C ₁ -C ₁₀ alkyl groups partially or completely substituted with halogen):

And X ² is a divalent organic group selected from the group consisting of a) a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, b) a substituted or unsubstituted Substituted C ₁ -C ₂₀ linear, branched, monocyclic or polycyclic alkylene groups, c) a substituted or unsubstituted heterocyclic group, d) a chain containing one or more An oxygen atom, a sulfur atom, or a linear or branched alkylene group of the NR ⁹¹ group, where R ⁹¹ is a C ₁ -C ₃ alkyl group, e) a structure IV ^a , IV ^b , or IV ^c divalent group f) A divalent group [A ^1- (B ¹ ) _n1 -A ² ], where n1 is an integer ranging from 1 to 5, and A ¹ and A ² are independently selected from the group consisting of: 1 . A substituted or unsubstituted C ₅ -C ₁₈ monocyclic or polycyclic aliphatic group, 2. A substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, And B ¹ is a bivalent linking group selected from the group consisting of: 1. a single bond, 2. a substituted or unsubstituted C ₁ -C ₂₀ linear, branched, monocyclic or polycyclic The alkylene group in the form of 3. A substituted or unsubstituted C ₂ alkenyl group, 4. A substituted or unsubstituted C ₂ alkynyl group, 5. A substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, 6. One oxygen atom, 7. One sulfur atom, 8. One-(C = O)-group, 9. One-[S (= O ) ₂ ]-group, 10. mono- (S = O)-group, 11. mono- [C (= O) O]-group, 12. mono- [C (= O) NH]-group Group, and 13. a-[O (C (R ⁵¹ ) ₂ C (R ⁵² ) ₂ O) _n2 ]-group, where n2 is an integer ranging from 1 to 6, and R ⁵¹ and R ^{52 are} independently based upon a hydrogen atom or a substituted or non-substituted C ₁ -C ₆ linear or points The alkyl group (e.g., a partially or fully substituted by halogen of C ₁ -C ₆ alkyl group), and Y is selected from the group consisting of a line Y ¹ and tetravalent organic radical of the group consisting of Y ² , Wherein Y ¹ is one or more of the structures Y ^1a -Y ^1d , wherein R ²² to R ^{30 are} independently H or a substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl group (For example, a C ₁ -C ₁₀ alkyl group partially or completely substituted with halogen):

And Y ² is a tetravalent organic group selected from the group consisting of: a) a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, b once substituted or unsubstituted the unsubstituted C ₂ -C ₁₈ linear, branched, monocyclic, or polycyclic alkyl group of the extension, c) a substituted or non-substituted heterocyclic group, d) a structure V ^a, V ^{b, V c, V d,} V e, V f, V g, V h, V i, or V ^j of the tetravalent group, wherein, R ³¹ to R ⁴¹ independently based a hydrogen atom or a substituted or unsubstituted A substituted C ₁ -C ₁₀ linear or branched alkyl group (for example, a C ₁ -C ₁₀ alkyl group partially or completely substituted with halogen), and L ³ to L ^{6 are} independently selected from An unsubstituted or substituted carbon atom, an oxygen atom, a sulfur atom, a-(C = O)-group, a-[S (= O) ₂ ]-group, and a-(S = O) -Group of groups: f) A tetravalent group [D ¹ -L ¹ -D ² ], wherein D ¹ and D ^{2 are} independently selected from the group consisting of: 1. C ₅ -C once substituted or unsubstituted ₁₈ monocyclic or polycyclic aliphatic groups, and 2. a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, and L ¹ is selected from the group consisting of Group of divalent linking groups: 1. a single bond, 2. a substituted or unsubstituted C ₁ -C ₂₀ linear, branched, cyclic or polycyclic alkylene group, 3. once substituted Or unsubstituted C ₂ alkenyl group, 4. a substituted or unsubstituted C ₂ alkynyl group, 5. a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic Groups, 6. One oxygen atom, 7. One sulfur atom, 8. One- (C = O)-group, 9. One- [S (= O) ₂ ]-group, 10. One- ( S = O)-group, 11. mono- [C (= O) O]-group, 12. mono- [C (= O) NH]-group, and 13. mono- [O (C ( R ⁶¹ ) ₂ C (R ⁶² ) ₂ O) _n2 ]-group, where n2 is an integer ranging from 1 to 6, and R ⁶¹ and R ^{62 are} independently a hydrogen atom or a substituted or unsubstituted C ₁ -C ₆ linear or branched alkyl group (for example, a part Or a C ₁ -C ₆ alkyl group completely substituted with halogen), wherein the molar percentage (X ¹ + Y ¹ ) is 25% of the total molar percentage (X + Y).

In another aspect, the present disclosure features a thermosetting composition comprising a polyimide polymer as described herein, at least one polyfunctional thiol compound containing at least dithiol groups; at least one solvent ; And optional At least one non-nucleophilic alkaline additive.

In some embodiments, the multifunctional thiol compound has the structure (VI): Where a is an integer ranging from 2 to 10; c is an integer ranging from 1 to 10; each of b, d, and e is independently an integer ranging from 0 to 1; f, g, and h Each is independently an integer ranging from 0 to 10; Q is a multivalent organic core; each of Z ¹ , W, and Z ¹¹ is independently a bivalent linking group; R ⁷¹ and R ⁷² Each is independently H, a substituted or unsubstituted C ₁ -C ₆ linear or branched alkyl group, or a substituted or unsubstituted C ₃ -C ₁₀ cycloaliphatic group; and M It is a substituted or unsubstituted C ₁ -C ₆ linear or branched aliphatic group, a substituted or unsubstituted C ₃ -C ₁₀ cycloaliphatic group, or a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group.

In some embodiments, the composition further includes at least one non-nucleophilic additive. For example, the non-nucleophilic basic additive may be a nitrogen-containing compound or a phosphorus-containing compound.

On the other hand, the present disclosure features a thermosetting composition comprising A. at least one polymer having structure I, B. at least one solvent, C. a selective non-nucleophilic alkaline additive, and D. At least one polyfunctional thiol having structure VI as described above, The condition is that the compound with structure VI does not contain an alkoxysilane group.

In another aspect, the present disclosure features a manufacturing method for manufacturing a thermosetting coating, which includes coating a substrate with a thermosetting composition disclosed herein to form a coated substrate, and baking the substrate Coated substrate to cure the thermosetting composition.

In another aspect, the present disclosure features a manufacturing method for manufacturing a thermosetting coating. The method includes: A. providing a substrate, B. coating the substrate with a thermosetting composition of the present disclosure to form a warp The coated substrate, and C. Baking the coated substrate at one or more temperatures for a time sufficient to cure the thermosetting composition.

In some embodiments, coating the substrate includes applying the thermosetting composition to the substrate by inkjet printing, spin coating, spray coating, dip coating, roller coating, or dynamic surface tension coating.

In another aspect, the present disclosure features a device (eg, a semiconductor device) that includes a coated substrate prepared by the manufacturing method described herein.

Detailed disclosure Definition of terms

In the context of this disclosure, the term "tetravalent group" used in connection with a polyimide polymer or a monomer synthesizing this polymer means that this element contains as part of the polymer backbone or After processing, it will become a part of the four bonds (quaternary) of an imide group. If allowed, other substituents may be present, but do not have a form that will be integrated into the main chain or amide imide group. The term "divalent group" means that this group connects two designated moieties. Any permissible substituents on this divalent group do not have the same pattern as the specified part.

The term "reverse addition ring reaction" refers to the reverse reaction of the cycloaddition reaction. An example of an anti-addition ring reaction is the retro-Diels-Alder reaction. In some embodiments, the products of the reverse addition ring-closing reaction can be formed on the basis of or simultaneously.

The terms "one or more" and "at least one" are used interchangeably. The terms "film" and "coating" are used interchangeably.

The terms "part" and "group" are used interchangeably. Similarly, equivalent singular systems can be used interchangeably.

Detailed description

The first embodiment of the present disclosure relates to the capped polyimide polymer of structure I.

Among them, Z is a divalent organic group capable of performing reverse addition ring-closing reaction (for example, in a solid state at a temperature of up to about 250 ° C), n is an integer greater than 5, and each X is independently selected from X ¹ and one or more of the divalent organic radical of the group of X ² wherein, X ¹ X -X architecture ^{1a 1d} one or more, wherein, R ¹¹ to R ²¹ are independently system H, a substituted or Unsubstituted C ₁ -C ₁₀ linear or branched alkyl groups (for example, C ₁ -C ₁₀ alkyl groups partially or completely substituted with halogen):

And X ² is a divalent organic group selected from the group consisting of a) a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, b) a substituted or unsubstituted Substituted C ₁ -C ₂₀ linear, branched, monocyclic or polycyclic alkylene groups, c) a substituted or unsubstituted heterocyclic group, d) a chain containing one or more An oxygen atom, a sulfur atom, or a linear or branched alkylene group of the NR ⁹¹ group, where R ⁹¹ is a C ₁ -C ₃ alkyl group, e) a structure IV ^a , IV ^b , or IV ^c divalent group f) A divalent group [A ^1- (B ¹ ) _n1 -A ² ], where n1 is an integer ranging from 1 to 5, and A ¹ and A ² are independently selected from the group consisting of: 1 . A substituted or unsubstituted C ₅ -C ₁₈ monocyclic or polycyclic aliphatic group, 2. A substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, And B ¹ is a bivalent linking group selected from the group consisting of: 1. a single bond, 2. a substituted or unsubstituted C ₁ -C ₂₀ linear, branched, monocyclic or polycyclic The alkylene group in the form of 3. A substituted or unsubstituted C ₂ alkenyl group, 4. A substituted or unsubstituted C ₂ alkynyl group, 5. A substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, 6. One oxygen atom, 7. One sulfur atom, 8. One-(C = O)-group, 9. One-[S (= O ) ₂ ]-group, 10. mono- (S = O)-group, 11. mono- [C (= O) O]-group, 12. mono- [C (= O) NH]-group Group, and 13. a-[O (C (R ⁵¹ ) ₂ C (R ⁵² ) ₂ O) _n2 ]-group, where n2 ranges from 1 to 6, and R ⁵¹ and R ^{52 are} independently a a hydrogen atom or a substituted or non-substituted C ₁ -C ₆ linear or branched alkoxy of Group (e.g., a partially or fully substituted with halogen or C ₁ -C ₆ alkyl group), and Y is independently selected from the group consisting of a line Y ¹ and tetravalent organic radical of the group consisting of Y ^2, Among them, Y ¹ is one or more of the structures Y ^1a -Y ^1d , wherein R ²² to R ^{30 are} independently a substituted or unsubstituted C ₁ -C ₁₀ linear, branched alkyl group (for example, C ₁ -C ₁₀ alkyl groups partially or completely substituted with halogen):

And Y ² is a tetravalent organic group selected from the group consisting of: a) a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, b once substituted or unsubstituted the unsubstituted C ₂ -C ₁₈ linear, branched, monocyclic, or polycyclic alkyl group of the extension, c) a substituted or non-substituted heterocyclic group, d) a structure V ^a, V ^{b, V c, V d,} V e, V f, V g, V h, V i, or V ^j of the tetravalent group, wherein, R ³¹ to R ⁴¹ independently based a hydrogen atom or a substituted or unsubstituted Substituted C ₁ -C ₁₀ linear or branched alkyl groups (for example, C ₁ -C ₁₀ alkyl groups partially or completely substituted with halogen), and L ³ to L ^{6 are} independently selected from An unsubstituted or substituted carbon atom, an oxygen atom, a sulfur atom, a-(C = O)-group, a-[S (= O) ₂ ]-group, and a-(S = O) -Group of groups: e) A tetravalent group [D ¹ -L ¹ -D ² ], where D ¹ and D ^{2 are} independently selected from the group consisting of: 1. C ₅ -C once substituted or unsubstituted ₁₈ monocyclic or polycyclic aliphatic groups, and 2. a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, and L ¹ is selected from the group consisting of Group of divalent linking groups: 1. a single bond, 2. a substituted or unsubstituted C ₁ -C ₂₀ linear, branched, cyclic or polycyclic alkylene group, 3. once substituted Or unsubstituted C ₂ alkenyl group, 4. a substituted or unsubstituted C ₂ alkynyl group, 5. a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic Groups, 6. One oxygen atom, 7. One sulfur atom, 8. One- (C = O)-group, 9. One- [S (= O) ₂ ]-group, 10. One- ( S = O)-group, 11. mono- [C (= O) O]-group, 12. mono- [C (= O) NH]-group, and 13. mono- [O (C ( R ⁶¹ ) ₂ C (R ⁶² ) ₂ O) _n2 ]-group, where n2 is an integer ranging from 1 to 6, and R ⁶¹ and R ^{62 are} independently a hydrogen atom or a substituted or unsubstituted C ₁ -C ₆ linear or branched alkyl group (for example, a part Or a C ₁ -C ₆ alkyl group completely substituted with halogen), wherein the molar percentage (X ¹ + Y ¹ ) is 25% of the total molar percentage (X + Y).

In some embodiments, the polymer of structure I can be prepared by the following three-step method. The first step is the polymerization of one or more diamines containing core X (as defined above) and one or more dianhydrides containing core Y (as defined above) to produce a polyamic acid (structure VII). The second step is that the polyamic acid is capped with a monoanhydride (as defined above) to produce the polyamic acid of structure VIII, which contains at least one compound capable of undergoing reverse addition ring-closing reaction (for example, in a solid state up to about 250 ° Temperature). The third step is the amide imidization of the end-capped polyamic acid of structure VIII to produce structure I. In some embodiments, the polymer of structure I can be prepared by other suitable methods.

The diamine containing core X is selected from diamines containing core X ¹ or X ² . The core X ¹ is selected from the group consisting of structures X ^1a- X ^1d containing an indane structure.

Among them, R ¹¹ -R ²¹ are as defined above.

X ^1a , an indane portion having a phenyl group, may be composed of any combination of groups of isomers of the chemical formula X ^1a or substituted isomers. Examples of the diamine containing the structure X ^1a need not necessarily include 5-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-tri Methyl indenane, 4-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindenane, and 5-amino -(1'-amino-2 ', 4'-dimethylphenyl) -1,3,3,4,6-pentamethylindenane.

X ^1b , an indane portion having a phenyl ether group, can likewise be composed of any combination of groups of isomers of the chemical formula X ^1b or substituted isomers. Examples of the diamine containing X ^1b need not include 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3- without limitation Trimethylindenane, and 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindenane.

X ^1c , which contains a diindenane moiety and an ether group in a helical relationship, may be composed of any combination of groups of isomers of the chemical formula X ^1c or substituted isomers. Examples of the diamine containing X ^1c need not include 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-helix without limitation Diindane and 6,6'-bis (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spiral indane.

X ^1d , an indane moiety, can likewise be composed of any combination of isomers of the chemical formula X ^1d or substituted isomers. Examples of the diamine containing X ^1d include, without limitation, 5,7-diamino-1,1-dimethylindenane, 4,7-diamino-1,1-dimethylindenane, 5,7-diamino-1,1,4-trimethylindenane, 5,7-diamino-1,1,6-trimethylindenane, and 5,7-diamino-1 , 1-dimethyl-4-ethyl indane.

An example of a preferred diamine containing one of X ^1a -X ^1d is 5-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3 -Trimethylindenane, 4-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane, 5-amine -(1'-Amino-2 ', 4'-dimethylphenyl) -1,3,3,4,6-pentamethylindenane, 5- (4-aminophenoxy)- 3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindenane, and 5- (3-aminophenoxy) -3- [4- (3 -Aminophenoxy) phenyl] -1,1,3-trimethylindane.

In certain embodiments, the diamine with core X ² has the general structure III.

Nucleus X ² is a divalent organic group selected from the group consisting of: a) a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, b) a substituted or unsubstituted Substituted C ₁ -C ₂₀ linear, branched, monocyclic or polycyclic alkylene group, c) a substituted or unsubstituted heterocyclic group, d) a chain containing one or more An oxygen atom, a sulfur atom, or a linear or branched alkylene group of the NR ⁹¹ group, where R ⁹¹ is a C ₁ -C ₃ alkyl group, e) a structure IV ^a , IV ^b , Or a divalent group of IV ^c f) A divalent group [A ^1- (B ¹ ) _n1 -A ² ], where n1 is an integer ranging from 1 to 5, and A ¹ and A ² are independently selected from the group consisting of: 1 . A substituted or unsubstituted C ₆ -C ₁₈ monocyclic or polycyclic alkylene group, 2. A substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, and B ¹ is a bivalent linking group selected from the group consisting of: 1. a single bond, 2. a substituted or unsubstituted C ₁ -C ₂₀ linear, branched, monocyclic or polycyclic Alkylene group, 3. a substituted or unsubstituted C ₂ alkenyl group, 4. a substituted or unsubstituted C ₂ alkynyl group, 5. a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, 6. an oxygen atom, 7. a sulfur atom, 8. a-(C = O)-group, 9. a- [S (= O) ₂ ]-group, 10. a- (S = O)-group, 11. a- [C (= O) O]-group, 12. a- [C (= O) NH]-group , And 13. a-[O (C (R ⁵¹ ) ₂ C (R ⁵² ) ₂ O) _n2 ]-group, where n2 ranges from 1 to 6, and R ⁵¹ and R ^{52 are} independently a hydrogen atom or a substituted or non-substituted C ₁ -C ₆ linear or branched alkyl group of Group (e.g., a partially or fully substituted with halogen or C ₁ -C ₆ alkyl group).

Examples of the divalent organic functional group B ¹ include without limitation both of the following: Among them, each of n3, n4, and n5 is independently an integer ranging from 1 to 6.

Suitable examples of linear or branched alkylene groups containing one or more oxygen atoms, sulfur atoms, or NR ⁹¹ groups in the chain include, without limitation Among them, R ⁹¹ is a C ₁ -C ₃ alkyl group (for example, methyl, ethyl, propyl, or isopropyl).

Suitable examples of X ² include the following chain segments without limitation:

Examples of suitable diamines having an X ² core include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,3-diamino-4,6-diisopropylbenzene, 2, 4-Diamino-1,3,5-trimethylbenzene, 3-methyl-1,2-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, m- Xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1 , 10-diaminodecane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexane bis (methylamine), 5-amino- 1,3,3-trimethylcyclohexanemethylamine, methaneamine, 2,5-diaminotrifluorotoluene, 3,5-diaminotrifluorotoluene, 1,3-diamino-2, 4,5,6-Tetrafluorobenzene, 4,4 'oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, 3,3'-diaminodiphenyl sulfone, 4 , 4'-Diaminodiphenyl sulfone, 4,4'-isopropyldiphenylamine, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) Propane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino Phenyl sulfone, 4-aminophenyl-3-aminobenzoate, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,2-bis [4- (4 -Aminophenoxyphenyl)) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,3-bis- (4-aminophenoxy) benzene, 1,3-bis- (3-aminophenoxy) benzene , 1,4-bis- (4-aminophenoxy) benzene, 1,4-bis- (3-aminophenoxy) benzene, 1- (4-aminophenoxy) -3- ( 3-aminophenoxy) benzene, 2,2'-bis- (4-phenoxyaniline) isopropylidene, N, N-bis (4-aminophenyl) aniline, bis (p-β -Amino-tert-butylphenyl) ether, p-bis-2- (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-amino (Pentyl) benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzophenone, 3'-dichlorobenzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 '-[1,3-phenylenebis (1-methyl- Ethylene)] bisaniline, 4,4 '-[1,4-phenylenebis (1-methyl-ethylene)] bisaniline 2,2-Bis [4- (4-aminophenoxy) phenyl] benzene, 2,2-bis [4- (3-aminophenoxy) benzene], 1,4-bis (4- Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,3'-bis (3-aminophenoxy) benzene, 2,6-diamino- 9H-thioxanthin-9-one, 2,6-diaminoanthracene-9,10-dione, and 9H-fluorene-2,6-diamine.

Examples of preferred diamines having an X ² core include m-phenylenediamine, 1,3-diamino-4,6-diisopropylbenzene, 2,4-diamino-1,3 without limitation , 5-trimethylbenzene, m-xylenediamine, 1,5-diaminonaphthalene, 2,5-diaminotrifluorotoluene, 3,5-diaminotrifluorotoluene, 4,4'- Oxydiphenylamine, 4,4'-diaminodiphenyl sulfone, 2,2-bis (4-aminophenyl) propane, 4-aminophenyl-3-aminobenzoate, 2, 2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2-bis (3-Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,3-bis- (4-aminophenoxy) benzene, 1,3-bis- (3 -Aminophenoxy) benzene, 1- (4-aminophenoxy) -3- (3-aminophenoxy) benzene, 2,2'-bis- (4-phenoxyaniline) Isopropyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzophenone, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 '-[1,3-phenylenebis (1-methyl-ethylene)] bisaniline, 4 , 4 '-[1,4-Phenylbis (1-methyl-ethylene)] bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] benzene, 2 , 2-bis [4- (3-aminophenoxy) benzene], 1,3'- (3-Aminophenoxy) benzene, 2,6-diamino-9H-thioxanthin-9-one, 2,6-diaminoanthracene-9,10-dione, and 9H-fluorene-2 , 6-diamine.

The dianhydride containing core Y is selected from dianhydrides containing core Y ¹ or Y ² . The core Y ¹ is selected from the group consisting of structures Y ^1a -Y ^1d (which contains an indane structure), wherein R ²² to R ^{30 are} independently H or a substituted or unsubstituted C ₁ -C ₁₀ linear 3. A branched alkyl group (for example, a C ₁ -C ₁₀ alkyl group partially or completely substituted with halogen).

Y ^1a , an indane moiety, may be composed of any combination of isomers of the chemical formula Y ^1a or substituted isomers. Examples of the dianhydride containing Y ^1a include 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindane-5,6-dicarboxylic dianhydride without limitation, 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindane-6,7-dicarboxylic dianhydride, 1- (3', 4'-dicarboxyphenyl ) -3-methylindenane-5,6-dicarboxylic dianhydride, and 1- (3 ', 4'-dicarboxyphenyl) -3-methylindan-6,7-dicarboxylic anhydride.

Y ^1b having an indane ether moiety may likewise consist of any combination of groups of isomers of the chemical formula Y ^1b or substituted isomers. Examples of the dianhydride containing Y ^1b include 5- [4- (1 ', 2'-dicarboxyphenoxy)]-3- [4- (1', 2'-dicarboxyphenoxy) without limitation ) Phenyl] -1,1,3-trimethylindane dianhydride, 5- [4- (2 ', 3'-dicarboxyphenoxy)]-3- [4- (2', 3 ' -Dicarboxyphenoxy) phenyl] -1,1,3-trimethylindane dianhydride, and 6- [4- (1 ', 2'-dicarboxyphenoxy)]-3- [4 -(1 ', 2'-dicarboxyphenoxy) phenyl] -1,1,3-trimethylindane dianhydride.

Y ^1c having a helix diindene moiety can also be composed of any combination of groups of isomers of the chemical formula Y ^1c or substituted isomers. Examples containing Y ^1c dianhydride include, without limitation, 6,6'-bis (3,4-carboxyphenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-helix Diindane tetracarboxylic dianhydride, 5,5'-bis (3,4-carboxyphenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spiral indane tetra Carboxylic dianhydride, and 5- (3,4-carboxyphenoxy) -6- (3 ', 4'-carboxyphenoxy)'-3,3,3 ', 3'-tetramethyl-1 , 1'-helix indane tetracarboxylic dianhydride.

Y ^1d , an indane moiety, may likewise consist of any combination of groups of isomers of the chemical formula Y ^1d or substituted isomers. Examples of the dianhydride containing Y ^1d include, without limitation, 1,2,3,4- (6,6-dimethylindenane) tetracarboxylic dianhydride, and 1,2,3,4- (7, 7-dimethyl indane) tetracarboxylic dianhydride.

Examples of preferred dianhydrides containing Y ¹ include without limitation 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindane-5,6-dicarboxylic acid bis Anhydride, 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindane-6,7-dicarboxylic dianhydride, 1- (3', 4'-dicarboxy Phenyl) -3-methylindane-5,6-dicarboxylic dianhydride, and 1- (3 ', 4'-dicarboxyphenyl) -3-methylindane-6,7-dicarboxy Acid anhydride.

In some embodiments, the dianhydride containing core Y ² has the general structure VI

Nucleus Y ² is a tetravalent organic group selected from the group consisting of: a) a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, b once substituted or unsubstituted Substituted C ₂ -C ₁₈ linear, branched, cyclic, or fused polycyclic alkylene groups, c) a substituted or unsubstituted heterocyclic group, d) a structure V ^a , V ^b , V ^c , V ^d , V ^e , V ^f , V ^g , V ^h , V ⁱ , or V ^j tetravalent group, wherein R ³¹ to R ^{41 are} independently a hydrogen atom or a A substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl group (for example, a C ₁ -C ₁₀ alkyl group partially or completely substituted with halogen), and L ³ to L ^{6 are} independently It is selected from an unsubstituted or substituted carbon atom, an oxygen atom, a sulfur atom, a-(C = O)-group, a-[S (= O) ₂ ]-group, and a- (S = O) -group consisting of groups:

e) A tetravalent group [D ¹ -L ¹ -D ² ], where D ¹ and D ^{2 are} independently selected from the group consisting of: 1. C ₅ -C once substituted or unsubstituted ₁₈ monocyclic or polycyclic aliphatic groups, and 2. a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group, and L ¹ is selected from the group consisting of Groups of divalent linking groups: 1. a single bond, 2. a substituted or unsubstituted C ₁ -C ₂₀ linear, branched, monocyclic, or polycyclic alkylene group, 3. A substituted or unsubstituted C ₂ alkenyl group, 4. A substituted or unsubstituted C ₂ alkynyl group, 5. A substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear Aromatic groups, 6. One oxygen atom, 7. One sulfur atom, 8. One- (C = O)-group, 9. One- [S (= O) ₂ ]-group, 10. One -(S = O)-group, 11. mono- [C (= O) O]-group, 12. mono- [C (= O) NH]-group, and 13. mono- [O ( C (R ⁶¹ ) ₂ C (R ⁶² ) ₂ O) _n2 ]-group, where n2 ranges from 1 to about 6, and R ⁶¹ and R ^{62 are} independently a hydrogen atom or a substituted or unsubstituted the C ₁ -C ₆ linear or branched alkyl group of (e.g., a The fully substituted by halogen or C ₁ -C ₆ alkyl group).

Examples of the divalent linking group L ¹ include without limitation the following: Among them, n3, n4 and n5 are as defined above.

Suitable examples of Y ² include the following chain segments without limitation:

Examples of suitable dianhydride monomers having a Y ² core include, without limitation, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 2,3,5,6-naphthalene tetra Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetra Carboxylic dianhydride, phenanthrene-, 8,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyridine -2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, butane-1 , 2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane Alkane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, drop Alkane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo [4.4.1.0 ^{2 , 5} .0 ^7,10 ] undecane-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2' , 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ash Tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ash tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ash tetracarboxylic dianhydride, 3,3 ' , 4,4'-Diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid Dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (dehydrated trimellitate), and 5- (2,5-dioxo Tetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

Examples of preferred dianhydrides with Y ² cores include pyridine without limitation -2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, drop Alkane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo [4.4.1.0 ^{2 , 5} .0 ^7,10 ] undecane-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3' , 4,4'-Diphenylbenzene tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid Acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydride trimellitate), and 5- (2,5-dioxane Substituted tetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

In some embodiments, the polymer of structure I may be a polymer mainly containing a repeating unit (for example, containing a portion formed by a condensation reaction between a diamine and a dianhydride). In these embodiments, the polymer of structure I can be obtained by using a diamine containing a core X (eg, X ¹ or X ² ) as defined above and a core Y (eg, Y ¹ or Y ² ) as defined above ) The dianhydride is used as the starting material, wherein at least one of the diamine and the dianhydride contains an indane-containing portion, which is then prepared with a monoanhydride end cap as defined above, and imidate. Exemplary monomer combinations that can produce polymers of structure I that mainly contain a repeating unit are shown in Table A below.

In some embodiments, the polymer of structure I may be a polymer mainly containing two or more different repeating units (for example, each containing a portion formed by a condensation reaction between a diamine and a dianhydride) Thing. In certain embodiments, the polymer of structure I can be obtained by using two or more diamines containing a core X (eg, X ¹ or X ² ) as defined above and a core containing a core Y (eg, Y) as defined above ¹ or Y ² ) dianhydride as a starting material, wherein at least one of the diamine and dianhydride contains an indane-containing portion, and thereafter, a monoanhydride end cap as defined above, and amide imine Chemically prepared. In certain embodiments, a polymer of structure I can be obtained by using a diamine containing a core X (eg, X ¹ or X ² ) as defined above and two or more cores containing a core Y (eg, Y ¹ or Y ² ) dianhydride as a starting material, wherein at least one of the diamine and the dianhydride contains a portion containing indane, and thereafter, a monoanhydride end cap and amide imide as defined above Chemically prepared. In some embodiments, a polymer of structure I can be obtained by using two or more diamines containing core X (eg, X ¹ or X ² ) as defined above and two or more diamines containing The dianhydride of the core Y (for example, Y ¹ or Y ² ) is used as a starting material, in which at least one of the diamine and the dianhydride contains a portion containing indane, and thereafter is terminated with a monoanhydride as defined above Covered and prepared by imidization. Exemplary monomer combinations that can produce polymers of structure I that mainly contain two or more repeating units are shown in Table A below.

The diamine monomer having the sub-structure X ¹ can be obtained by, for example, the synthesis methods detailed in US3,856,752, US3,983,092, JP61-254543 and US4,734,482, or others known to those skilled in the art Prepared by universal organic synthesis methods. The dianhydride monomer having the substructure Y ¹ can be prepared by, for example, the synthesis methods detailed in US 3,856,752 and US 5,047,487, or by other general organic synthesis methods known to those skilled in the art. ² of diamine monomer and the dianhydride monomer system ² having the Y-order structure having a plurality of secondary structure X may be commercially available from various sources, comprising Chriskev Company (Lenexa, Kansas, USA ), or additionally via the person skilled in the art Known by general organic synthesis methods.

Polyamides of structure VII can be synthesized by various synthetic procedure variants of procedures known to those skilled in the art. Generally, the synthetic procedure is to contact one or more diamines with one or more dianhydrides in the presence of a polyamic acid formed in a solvent suitable for dissolving these monomers and preferably formed.

In some embodiments, for the preparation of polyamic acid, the diamine component and the dianhydride component are gradually injected by the method of injecting these components at the same time or the solid or solution type of these components gradually The method of pouring into the solution of other components (all materials may not completely dissolve) and pouring into a reaction vessel. In terms of productivity, the method of injecting these two components simultaneously is advantageous because the time required for injection is shortened. The molar ratio of the diamine component to the dianhydride component is preferably between 1.01 and 1.40. More preferably, a molar ratio of diamine to dianhydride of about 1.05 to 1.33 is used. Generally, the reaction is carried out at about 15 ° C to about 80 ° C for about 1 to about 48 hours. Note that when the molar ratio of the diamine component to the dianhydride component The rate is greater than 1.00. The formed species is a polyamino acid with an amine group as the terminal, which can be further reacted with a capping monomer at the end (for example, a monoanhydride containing a group capable of undergoing reverse addition ring bonding reaction) to form a End cap polymer.

Suitable polymerization solvents usable in the present invention include, without limitation, N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, N , N-dimethylacetamide, tetramethylmethine, p-chlorophenol, m-cresol, diethylene glycol methyl ether, methyl-3-methoxypropionate, ethyl-3-ethoxy Propionate, cyclohexanone, propylene glycol monomethyl ether acetate, and 2-chloro-4-hydroxytoluene. These solvents may be used alone or in combination of two or more. Among these solvents, N-methyl-2-pyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferred, and N-methyl-2-pyrrolidone is more preferred. good. In some embodiments, one of the poor solvents of polyimide may be used in combination with these solvents in an amount that does not precipitate polyamic acid. Examples of such a poor solvent include hexane, heptane, benzene, toluene, xylene, chlorobenzene, and o-dichlorobenzene. Based on the total amount of these solvents, the amount of lean solvent used is preferably 50% by weight or less (including 0). The manufactured polyamide can be isolated by precipitation in a non-solvent or a poor solvent, and collected by filtration.

The second step of the above method for synthesizing the polymer of structure I is to end cap the polyamide of structure VII synthesized in the first step. In some embodiments, the second step may be performed by reacting the amino-terminated polyamic acid of structure VII with the monoanhydride of structure IX to produce the capped polyamic acid of structure VIII. In some embodiments, the thus formed capped polyamide can be used for further reaction without isolation.

In some embodiments, the monoanhydride suitable for the preparation of the polyamic acid of structure VIII contains a "masked" maleic anhydride group, which becomes an "imide" group after the anhydride group is converted The "masked" maleimide group. This amide imide group in the polymer of structure I can undergo an anti-addition ring reaction (eg, retro Diels Alder) to demask the maleimide group. Polyimide polymers containing maleimide groups as end groups can react with a crosslinking agent (for example, a compound containing at least two thiol groups) to form a crosslinked polyimide amine.

Examples of monoanhydrides that can undergo reverse addition ring-closing reactions include, without limitation, the compounds described in Structure IX.

Among them, G series -O-,-(NR ¹⁰⁰ )-,-[C (R ¹⁰¹ ) = C (R ¹⁰² )]-, or-[C = C (R ¹⁰³ ) ₂ ]-, where, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , and R ^{103 are} each independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic or polycyclic alkyl group, or a substituted Or unsubstituted phenyl group, and each of R ¹ , R ² , R ³ and R ⁴ is independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic Or polycyclic alkyl group, a substituted or unsubstituted phenyl group, OR ¹⁰⁴ , CH ₂ OR ¹⁰⁵ , CH ₂ OC (= O) R ¹⁰⁶ , CH ₂ C (= O) OR ¹⁰⁷ , CH ₂ NHR ¹⁰⁸ , CH ₂ NHC (= O) R ¹⁰⁹ , CH ₂ C (= O) N (R ¹¹⁰ ) ₂ , C (= O) OR ¹¹¹ , where R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , and R ^{111 are} each independently H or a substituted or unsubstituted C ₁ -C ₆ linear, branched, or monocyclic alkyl group.

Examples of anhydrides of structure IX include structures IX ^a , IX ^b , IX ^c , or IX ^d without limitation: Among them, R ¹ -R ⁴ and R ¹⁰⁰ -R ¹⁰³ are as defined above.

Examples of structures IX that are particularly suitable for monoanhydrides include, without limitation, the following Column compound.

Generally, the reaction of the polyamic acid of structure VII with the monoanhydride of structure IX is carried out in the presence of a basic catalyst at about 10 ° C to about 70 ° C for about 3 to about 48 hours. Examples of suitable basic catalysts include, without limitation, pyridine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, 2-picoline, 2,6-lutidine, 3,5-di Picoline, picoline, 4-dimethylaminopyridine (DMAP), etc. In general, the basic catalyst should not be a compound that will degrade the polyamide backbone. Examples of compounds capable of degrading the main chain of polyamic acid include, without limitation, primary and secondary amines. The amount of monoanhydride used is about 1.01 to the theoretical unreacted amine functionality on the amine-terminated polyamic acid 1.25 molar equivalent. Preferably, the amount of monoanhydride used is about 1.01 to 1.15 mole equivalents of unreacted amine functionality on the amine-terminated polyamic acid. More preferably, the amount of monoanhydride used is about 1.05 to 1.10 molar equivalents of unreacted amine functionality on the amine-terminated polyamic acid. Monoanhydride is added to the reaction mixture as a solid or as a solution in a suitable solvent. The preferred solvent is the reaction solvent. The basic catalyst is typically added to the polyamic acid solution after adding the monoanhydride. Preferably, the basic catalyst can be used in the same molar equivalent as the monoanhydride used in the reaction mixture.

In some embodiments, in the third step of the synthesis method of structure I, a chemical amide imidization agent (dehydrating agent) is added to the end-capped polyamic acid of structure VIII, which catalyzes the polyamic acid group The closed-loop dehydration method forms the functionality of the amide imide on the main chain and the end cap group, thereby forming the end-capped polyimide.

Examples of suitable dehydrating agents include, without limitation, trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, ethanesulfonic acid, butanesulfonic acid, perfluorobutanesulfonic acid, acetic anhydride, propionic anhydride, and Butyric anhydride. In addition, this dehydration method can be catalyzed by further adding a basic catalyst. If used, the basic catalyst used may be the same as or different from the basic catalyst used for the end cap reaction as described above.

In some embodiments, the chemical amide imine method is performed at about 60 ° C to about 130 ° C for about 6 to about 48 hours with a suitable dehydrating agent and a basic catalyst. Dehydrating agents and basic catalysts are typically used at equal molar concentrations. Based on the total amidic acid present in the polymerization mixture, about 90 to 200% (mole) of dehydrating agent is typically used to complete the cyclization reaction. Preferably, 120 to 160% (mole) of dehydrating agent is used to complete the cyclization of amidic acid.

Evidence for the completion of amide imine and the formation of structure I polyimide can be confirmed by observing the characteristic absorption of the amide imide ring structure in the infrared spectrum from 1770 to 1700 cm ^-1 .

In some embodiments, the formed polyimide of structure I can be isolated by precipitation in water and / or organic solvents, recovered by filtration, and dried. In addition, the polyimide of structure I can be isolated by adding water and a suitable low-boiling water-immiscible solvent. Because of the lower polar nature of the indane portion in the polyimide polymer, unlike most polyimides, the higher solubility in water-immiscible solvents of lower polarity can make the polyimide Extracted from higher polarity reaction solvent / water mixture. This extracted polymer solution can be purified by washing with water and then separating the water layer, distilling various volatile compounds, and then extracting it in a higher boiling point solvent. Preferably, the higher boiling point solvent is also the precipitation solvent for the composition of the present disclosure.

It should be noted that the molecular weight of the polymer, as well as the inherent viscosity and therefore the fixed stoichiometry of X and Y, can have reaction criteria and considerations (such as solvent purity, humidity, presence or absence of nitrogen or argon layers, Reaction temperature, reaction time, and other variables). However, these factors need to be controlled in order to achieve a polymer with the desired amount of indane structure and molecular weight.

Generally, the molar amount (X ¹ + Y ¹ ) of the indane structure in the polymer of structure I needs to be in the range of (X + Y) from 25 mol% to about 100 mol%. In some embodiments, the molar amount of (X ¹ + Y ¹ ) ranges from about 25% (eg, about 35%, about 45%, or about 50%) to about 60% (eg, about 70%, About 85%, or about 100%). The molar amount (X ¹ + Y ¹ ) ranges from about 25% (eg, about 30%, about 35%, or about 40%) to about 45% (eg, about 50%, about 55) in certain embodiments %, Or about 60%). In some embodiments, the molar amount of (X ¹ + Y ¹ ) ranges from about 35% (eg, about 45%, about 55%, or about 65%) to about 70% (eg, about 85%, About 95%, or about 100%). In some embodiments, the molar amount of (X ¹ + Y ¹ ) ranges from about 50% (eg, about 55%, about 60%, or about 65%) to about 70% (eg, about 80%, About 90%, or about 100%).

In some embodiments, the X ¹ range is from 0% (eg, about 5%, about 15%, about 20%, or about 30%) of the molar amount of (X + Y) to about 58.3% (eg, About 50.5%, about 45%, about 40%, or 35%).

In certain embodiments, Y ¹ ranges from 0% (eg, about 10%, about 20%, about 30%, or about 35%) to about 49.5% (eg, About 49%, about 41.7%, about 35%, or about 25%).

As mentioned previously, the indane structure can be incorporated into the polymer backbone via the diamine monomer (X ¹ ) or dianhydride monomer (Y ¹ ). In some examples, it is preferred that the indane substructure is incorporated exclusively via X ¹ , exclusively via Y ¹ , or via a combination of X ¹ and Y ¹ . When a combination of X ¹ and Y ¹ is used, the suitable ratio of X ¹ : Y ¹ ranges from about 99: 1 to about 1:99. Another suitable range is from about 90:10 to about 10:90, from about 80:20 to about 20:80, from about 75:25 to about 25:75, from about 65:35 to about 35:65, from about 60:40 to about 40:60, and about 50:50.

The amount of (X + Y) can be calculated by dividing the number average molecular weight (Mn) of the polymer of structure I by the average molecular weight of the repeating unit. The value of Mn can be determined by, for example, Jan Rabek, Experimental Methods in Polymer Chemistry, John Wiley & Sons, New York, 1983 The membrane osmotic pressure measurement method or gel osmosis chromatography standard method is used for determination.

The suitable weight average molecular weight (Mw) of the polyimide of structure I ranges from about 1,000 g / mole to about 50,000 g / mole. The preferred molecular weight range may depend on the particular product application, the solvent used, and the method of application to the underlying substrate. For example, a suitable weight average molecular weight value for inkjet coating may be at least about 1,000 g / mole (eg, at least about 9,000 g / mole, at least about 12,000 g / mole, at least about 15,000 g / mole, At least about 20,000 g / mole, at least about 25,000 g / mole, or at least about 35,000 g / mole) and / or may be up to about 50,000 g / mole (eg, up to about 40,000 g / mole, up to about 35,000 g / mole, up to about 30,000 g / mole, up to about 25,000 g / mole, up to about 20,000 g / mole, up to about 15,000 g / mole, up to about 12,000 g / mole). In some embodiments, n in structure I is an integer greater than 5 (eg, from 6 to 50, from 6 to 30, from 10 to 50, or from 10 to 30).

In some embodiments, the polymer of structure I has the following structure (structure II).

Among them, n, X, Y, G, and R ¹ -R ⁴ are as defined above. In some embodiments, the polymer of structure II is synthesized using the following combination: one or more X ¹ containing monomers selected from the group consisting of And / or one or more X ² containing monomers selected from the group consisting of Y ^{1 with} monomers containing the following structure And / or one or more Y ² containing monomers selected from the group consisting of With one or more monoanhydrides selected from the group consisting of Among them, the percentage of mole (X ¹ + Y ¹ ) is 25% of the total molar percentage (X + Y), and the X: Y ratio is from about 1.01 to about 1.4. Special examples of some combinations of these embodiments are shown in Table A below.

The polyimide polymers described herein generally have excellent solubility in organic solvents (including solvents of lower polarity. In particular, this results in inkjet coating that is superior to polyimide compositions of conventional techniques Improved performance because the polyimide polymer described here provides more flexibility in solvent selection, can easily adjust the viscosity of the thermosetting solution, increase the amount of polymer applied per drop, and minimize clogging of the inkjet nozzle, and Maximize the amount of downtime allowed between coating periods without blocking the inkjet nozzles.

The disclosure also relates to a thermosetting composition comprising A. at least one polyimide polymer described herein (eg, a polymer of structure I), B. at least one solvent, C. selective A non-nucleophilic basic additive, and D. at least one polyfunctional thiol compound containing at least two thiol groups (which can act as a crosslinking agent), such as a compound of structure VI, Where a is an integer ranging from 2 to 10; c is an integer ranging from 1 to 10; each of b, d, and e is independently an integer ranging from 0 to 1; f, g, and h Each is independently an integer ranging from 0 to 10; Q is a multivalent organic core; each of Z ¹ , W, and Z ¹¹ is independently a bivalent linking group; R ⁷¹ and R ⁷² Each is independently H, a substituted or unsubstituted linear or branched C ₁ -C ₆ alkyl group, or a substituted or unsubstituted C ₃ -C ₁₀ cycloaliphatic group; and M is A substituted or unsubstituted C ₁ -C ₆ linear or branched aliphatic group, a substituted or unsubstituted C ₃ -C ₁₀ cycloaliphatic group, or a substituted or unsubstituted C _6- C ₁₈ mononuclear or polynuclear aromatic group. In some embodiments, the compound of structure VI does not contain alkoxysilane groups.

Generally, a ranges from 2 (eg, 3, 4, 5, 6) to 10 (eg, 9, 8, 7, 6), and f, g, and h independently range from 0 (eg, 1, 2, 3, 4, 5) to 10 (for example, 9, 8, 7, 6, 5), and c ranges from 1 (for example, 2, 3, 4, 5) to 10 (for example, 9, 8, 7, 6).

Examples of Z ¹ and Z ¹¹ include -O-, -S-, -O- (C = O)-,-(C = O)-,-(C = O) -O-, -NH without limitation -(C = O)-, and-(C = O) -NH-.

The divalent organic bridging group, W, is a bridging group that connects Q via Z ¹ and Z ¹¹ to a thiol group or other organic functional group. Preferably, W is selected from the group consisting of: 1. A substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic, or polycyclic alkylene group, which is selectively Contains one or more oxygen, sulfur, or nitrogen atoms; 2. A substituted or unsubstituted phenylene; 3. A substituted or unsubstituted C containing one or more oxygen, sulfur, or nitrogen atoms ₃ -C ₆ mononuclear heteroaryl; 4. A substituted or unsubstituted C ₁₀ -C ₃₀ polynuclear aryl; and 5. A substituted or containing one or more oxygen, sulfur, or nitrogen atoms Unsubstituted C ₇ -C ₃₀ polynuclear heteroaryl.

Preferably, Q is selected from the group consisting of: 1. an unsubstituted C ₂ -C ₄₀ linear, branched, monocyclic, or polycyclic aliphatic group, which optionally contains One or more oxygen, sulfur, or nitrogen atoms; and 2. An unsubstituted C ₂ -C containing cyclic and acyclic components and optionally containing one or more oxygen, sulfur, or nitrogen atoms ₄₀ aliphatic groups. Examples of Q include without limitation

Some examples of special thiol compounds in thermosetting compositions suitable for the present disclosure include, without limitation, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane Tris (3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tris [2- (3-mercaptopropionyloxy) ethyl] iso Cyanurate, ethoxylated trimethylolpropane tri-3-mercaptopropionate, propylene glycol-3-mercaptopropionate 800, trimethylolpropane tris (4-sulfanylcyclohexane carboxyl Acid ester), pentaerythritol tetrakis (4-sulfanylcyclohexane carboxylate), etc.

Suitable solvents for this thermosetting composition may include alcohols, ketones, lactones, ethers, amides, amides, and esters. The solvent typically needs to dissolve the thermosetting composition All components of the substance are cast into a good film, and should not interfere with the cross-linking reaction of the composition. Suitable examples of organic solvents include, without limitation, γ-butyrolactone (GBL), N-methyl-2-pyrrolidone, dimethyltetrahydroimidazolone, N-methylcaprolactam, N-methyl Acylamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide , Methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, n-butyl acetate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), lactic acid Ethyl acetate, propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether ether Ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, 3-ethoxypropyl Ethyl acetate, diethyl malonate, ethylene glycol 1,4: 3,6-dianhydrosorbitol 2,5-dimethyl ether (2,5-dimethyl isosorbide), 1,4: 3,6-dianhydrosorbitol 2,5-diethyl ether (2,5-diethyl isosorbide), and mixtures of these. More preferred solvents are γ-butyrolactone, propylene glycol monomethyl ether, 2-heptanone, propylene glycol monomethyl ether acetate, n-butyl acetate, ethyl lactate, and cyclohexanone. These solvents can be used individually or in combination of two or more to improve the coating quality of the thermosetting composition.

The choice of the solvent and its concentration for the thermosetting composition depends mainly on the coating method used and the solid used in the formulation. The solvent needs to be inert (for example, it should not undergo any chemical reaction with the components) and needs to be removable when dried after coating. In the thermosetting composition of the present disclosure, the amount of a solvent or solvent mixture as a component of the entire composition may be at least about 40% by weight of the entire mass of the thermosetting composition. For example, using a thermosetting composition Based on individual mass, the amount of solvent or solvent mixture may range from about 40 to about 98% by weight (eg, from about 85% to about 98% by weight, from about 88% to about 97% by weight, from about 90 Weight percent to about 95 weight percent, from about 50 weight percent to about 97 weight percent, or from about 60 weight percent to about 96 weight percent).

In certain embodiments, the amount of the polyimide polymer described herein in a single solvent or solvent mixture is from about 1% to about 50% by weight of the total weight of the composition (eg, from about 1% by weight To about 10% by weight, from about 1.5% to about 8% by weight, from about 2% to about 6% by weight, from about 5% to about 50% by weight, from about 10% to about 45% by weight, Or from about 20% to about 45% by weight). Generally, the weight percentage of the polyimide polymer in a formulation depends on the coating method used for the thermosetting composition. The polyimide polymers described herein can be used in a thermosetting composition alone or in any combination of seven ratios.

In certain embodiments, the amount of polyfunctional thiol compound ranges from about 0.2% to about 30% by weight of the total weight of the thermosetting composition (eg, from about 0.2% to about 6% by weight, from about 0.5% by weight % To about 4% by weight, from about 0.8% to about 3% by weight, from about 1% to about 30% by weight, from about 2% to about 25% by weight, or from about 5% to about 25% by weight %).

The thermosetting composition of the present disclosure can optionally contain at least one non-nucleophilic additive. One purpose of this non-nucleophilic additive is to act as a catalyst to assist in the thermal curing of the coating during the final baking step, so that the curing is completed at a lower temperature. In general, the nucleophilic nature of the basic additive needs to be a low degree that will not initiate a nucleophilic attack on the amide imide group of the polyimide. In some embodiments, when present, the non-nucleophilic alkaline addition in the thermosetting composition The total amount of agent is from about 0.002 wt% to about 2 wt% of the total composition (eg, from about 0.002 wt% to about 0.4 wt%, from about 0.01 wt% to about 0.2 wt%, from about 0.01 wt% to About 2% by weight, or from about 0.05% to about 1% by weight).

In some embodiments, the non-nucleophilic basic additive is selected from the group consisting of: a) non-nucleophilic nitrogen-containing basic compounds, and b) non-nucleophilic phosphorus-containing basic compounds.

In some embodiments, the non-nucleophilic nitrogen-containing basic compound is selected from the group consisting of: a) non-nucleophilic amines, b) non-nucleophilic amidines, and c) non-nucleophilic amidines Imines.

In some embodiments, the non-nucleophilic phosphorus-containing basic compound is selected from the group consisting of: a) non-nucleophilic phosphines, b) non-nucleophilic phosphites, c) non-nucleophilic phosphites Phosphorus-containing bicyclic organic nonionic superbases (proazaphosphatranes), and d) Non-nucleophilic azophosphonases

Examples of suitable non-nucleophilic nitrogen-containing basic compounds include, without limitation, N, N-dicyclopentylmethylamine, N, N-dicyclopentylethylamine, N, N-dimethylcyclohexylamine , N, N-dicyclohexylmethylamine, N, N-dicyclohexylethylamine, N, N-dicyclohexylbutylamine, N, N-dicyclohexyl third butylamine, 1-dimethylamine fund Steel ane, 1-diethylamine fund steel ane, 2-dimethyl amine fund steel ane, 2-methylimidazole, triethylamine, tripropylamine, tributylamine, triisopropylamine, trihexylamine, trioctyl Amine, tridodecylamine, 2,4,5-triphenylimidazole, 1,4-diazabicyclo [4.3.0] non-5-ene, 1,5-diazabicyclo [4.3. 0] Non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,1,3,3-tetramethylguanidine, pyridine, 2-methylpyridine, 2 , 6-lutidine, 3,5-lutidine, 1,4-diazabicyclo [2.2.2] octane, and picoline. Examples of suitable non-nucleophilic phosphorus-containing basic compounds include, without limitation, N'-third butyl-N, N, N ', N', N ", N" -hexamethyliminophosphoric acid triphosphate Acetamide, 2-tributylbutylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphine, tertiary octylimino -Tris (dimethylamino) phosphane, tertiary butylimino-tris (pyrrolidinyl) phosphane, 2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3 ] Undecane, 2,8,9-tris (1-methylethyl)], and 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phospha Bicyclic [3.3.3] undecane.

In some embodiments, non-nucleophilic alkaline additives can be thermally and / or photochemically active. These thermally activated persons are called thermal base generators (TBG), and these photochemically activated persons are called photobase generators (PBG). If so, those skilled in the art will know the appropriate TBG and / or PBG (if any) to be used in the composition of this disclosure.

Other additives such as adhesion promoters, surfactants, and plasticizers (but not limited to these) may be added to the thermosetting composition. In addition, the amount of additives may range from 0% to about 15%.

Suitable adhesion promoters are described in "Silane Coupling Agent" Edwin P. Plueddemann, 1982 Plenum Press, New York. The types of adhesion promoters include vinyl alkoxysilanes and Acryloyloxyalkoxysilanes (for example, 3-methacryloyloxypropyldimethoxymethylsilane, and 3-methacryloyloxypropyltrimethoxysilane), mercaptoalkanes Oxysilanes, aminoalkoxysilanes, epoxyalkoxysilanes, and oxidized glycidylalkoxysilanes.

Examples of suitable adhesion promoters that can be used in thermosetting compositions can be described in Structure XIV.

Where each R ⁸¹ and R ^{82 is} independently a substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl group or -C ₃ -C ₁₀ cycloalkyl group, p is from 1 to 3 Integer, and n6 is an integer from 1 to 6, R ⁸³ is one of the following: Wherein, each R ⁸⁴ , R ⁸⁵ , R ⁸⁶ and R ^{87 is} independently a C ₁ -C ₄ alkyl group or a C ₅ -C ₇ cycloalkyl group. A preferred adhesion promoter is one in which R ⁸³ is selected from the following:

Examples of suitable adhesion promoters having the structure XIV include, without limitation, γ-aminopropyltrimethoxysilane, γ-oxyglycidylpropylmethyldimethoxysilane, γ-oxyglycidylpropyl Methyldiethoxysilane, oxidized glycidylpropyltrimethoxysilane, and γ-mercaptopropyl-methyldimethoxysilane.

In some embodiments, the adhesion promoter contains a thiol-free silicon compound. In some embodiments, the adhesion promoter contains a silicon compound free of acrylic acid. In some embodiments, the adhesion promoter contains an epoxy-free silicon compound.

In some embodiments, if used, the concentration of the selective adhesion promoter ranges from about 0.02% to about 5% by weight of the total weight of the thermosetting composition (eg, from about 0.02% to about 1% by weight, From about 0.04 wt% to about 0.5 wt%, from about 0.06 wt% to about 0.4 wt%, from about 0.1 wt% to about 5 wt%, from about 0.2 wt% to about 1.5 wt%, or from about 0.3 wt% To about 1% by weight).

The thermosetting composition of the present disclosure can also optionally contain at least one surfactant. If a surfactant is used, based on the total weight of the thermosetting composition, it may be added from about 0.001 to about 2% by weight and preferably from about 0.01 to about 1% by weight. Examples of suitable surfactants include without limitation Contained in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, The surfactants described in JP-A-8-62834, JP-A-9-54432 and JP-A-9-5988.

Examples of suitable nonionic surfactants include, without limitation, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether ; Polyoxyethylene alkyl allyl ether, such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene copolymer; sorbitol fatty acid esters, such as sorbitol monolaurel Ester, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol fatty acid ester , Such as, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol Three stearates.

The commercially available fluorine- or silicon-containing surfactants include Eftop EF301, EF303 (manufactured by Shin-Akita Kasei KK) without limitation; Megafac F171, F173, F176, F189, R08 (manufactured by Dainippon Ink & Chemicals Inc. Manufactured); Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.); and Troysol S-366 (manufactured by Troy Chemical KK). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-containing surfactant.

In some embodiments, the thermosetting composition may optionally contain One less plasticizer. If used, the concentration of this selective plasticizer may range from about 1% to about 10% by weight of the total weight of the thermosetting composition. The preferred amount of plasticizer may be from about 2% to about 10% by weight.

Generally, the plasticizer needs to have a lower volatility than the solvent used at a typical baking temperature of about 70 ° C to about 150 ° C, so that it remains in the film after the first baking step. This typically means that the plasticizer of the present invention has a higher boiling point than the solvent used unless the interaction of the functional group of the plasticizer with other components of the thermosetting composition sufficiently reduces its volatility. Examples of plasticizers include, without limitation, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, tripropylene glycol, polypropylene glycol, glycerin, butylene glycol, hexylene glycol, sorbitol, cyclohexane di Alcohol, 4,8-bis (hydroxymethyl) -tricyclo (5.2.1.0,2,6) decane, and 2-oxoheptanone and 2-ethyl-2- (hydroxymethyl) -1,3 -Propylene glycol copolymer. Preferred polyhydroxy compounds having at least two hydroxyl groups are diethylene glycol, tripropylene glycol, and copolymers of 2-oxanone and 2-ethyl-2- (hydroxymethyl) -1,3-propanediol . The preferred saturated glycol monoethers are tripropylene glycol, triethylene glycol, and tetraethylene glycol saturated monoethers.

Although other reactions may occur and do not wish to be bound by theory, it is believed that the thermal recycling of the polyimide described herein can occur by the mechanism illustrated in Scheme 1.

The polyimide described here is one of the essential components of the thermosetting composition and has the "masked" terminal group of the maleimide group. Maleimide can react rapidly with thiols through the addition reaction of SH group across the C = C double bond of maleimide in solution under ambient conditions. One of the key aspects of this disclosure is that the polyimide described here contains polymer end groups, which are not free maleimide, but as latent or "masked" maleimide, In order to maintain the solubility of the solution during the storage life of the product. When heated to a sufficient temperature (for example, up to about 250 ° C), the polymer terminal groups undergo a reverse-addition ring (for example, reverse Diels Alder (rDA)) reaction to demask the maleimide group, It is now reactive towards thiol groups. Because the reaction of thiol-maleimide in the membrane (ie, solid state) is lower than in solution, selective non-nucleophilic alkaline additives can be added to help reduce the formation for curing The temperature required for an insoluble cross-linked material.

Generally, in order to minimize the shrinkage of the film during curing, the compound or these compounds formed by reverse addition ring-closing reaction need to represent a small percentage of the total film mass, or these compounds need to be converted into this final bake through other thermal reactions An integral part of the baked film. If this part does not become an integral part of the final baking film, it needs to be volatile and leave the film completely in the final baking step. This ensures that no part is released from the final baked film over time.

The disclosure also relates to a manufacturing method for manufacturing thermosetting coatings. In some embodiments, the method includes a) coating a substrate with a thermosetting composition of the present disclosure to form a coated substrate, and b) baking the coated substrate (eg, in a Temperature or temperature Continue for a period of time) to cure this thermosetting composition.

In another embodiment, the disclosure also relates to a manufacturing method for manufacturing a thermosetting coating, which includes: a) providing a substrate, b) coating a substrate with a thermosetting composition of the disclosure A coated substrate, c) in a first baking step, baking the coated substrate at a temperature T ₁ to remove most of the solvent, and d) in a second baking step, in Baking the coated substrate at a temperature T ₂ to cure the coating (for example, the coating becomes insoluble in an organic solvent), where T ₁ 150 ℃, 180 ℃ T ₂ 250 ° C, and the total film thickness loss from step c to step d is <10%.

The substrate may be, for example, a semiconductor material, such as a silicon wafer, a compound semiconductor (Group III-V) or (Group II-VI) wafer, a ceramic, a glass, or a quartz substrate. The substrate may also contain films or structures used in the manufacture of electronic circuits, such as organic or inorganic dielectrics, or copper or other wiring metals.

The manufacturing method can optionally include the step of pre-wetting a substrate with a solvent. Any suitable method known to those skilled in the art for treating the substrate with a solvent can be used. Examples include treating the substrate with a solvent by spraying, flowing, or dipping the substrate with a solvent. The processing time and temperature will depend on the specific substrate and method, which can use high temperatures. Any suitable solvent or solvent blend can be used. The preferred solvent is the one used in the thermosetting composition of the present disclosure.

The method may optionally include pre-coating a substrate with a solution containing an adhesion promoter. Any suitable method known to those skilled in the art for treating this substrate with an adhesion promoter can be used. Examples include treating the substrate with vapor, solution or 100% concentration of the adhesion promoter. The processing time and temperature will depend on the specific substrate, adhesion promoter, and method, which can be used at high temperatures. Any suitable external adhesion promoter can be used. Suitable types of external adhesion promoters include, without limitation, vinyl alkoxy silanes, methacryl alkoxy alkoxy silanes, mercapto alkoxy silanes, amino alkoxy silanes, epoxy Alkoxysilanes, and glycidyloxyalkoxysilanes.

In some embodiments, one thermosetting composition of the present disclosure is coated on a suitable substrate to form an unbaked coated substrate. The coating method for the thermosetting composition includes, without limitation, spray coating, spin coating, lithography, inkjet printing, roll coating, screen printing, extrusion coating, curved coating, curtain coating Coating, and wet stain coating. Other techniques, such as direct injection of fluid from individual units or continuous jet of fluid to a surface, can also be used. The parameters used for coating will depend on the specific coating tool and are well known in the art.

In a preferred embodiment, the thermosetting composition can be deposited on a substrate surface using various low viscosity deposition tools. The low viscosity deposition tool is a device that deposits a dilute solution on a surface by spraying the solution onto the surface through an orifice, and the tool is not in direct contact with the surface. A preferred direct writing deposition tool is an inkjet device, such as a piezoelectric, thermal, drop-on-demand or continuous inkjet device. Other examples of direct writing deposition tools Airborne suspension jets and automatic syringes, such as the MICROPEN tool available from Ohmcraft, Inc. (Honeoye Falls, NY).

Regardless of the coating method used, after the thermosetting composition is applied to a substrate, the unbaked coated substrate is typically heated at a high temperature using a baking device. Any suitable baking device can be used. Examples of suitable baking devices include, without limitation, hot plates, infrared lamps, convection ovens, and thermal heating elements on inkjet printheads.

In one embodiment, the unbaked coated substrate is baked using a baking device at a suitable temperature in a single-step method. In these embodiments, the baking temperature may range from about 180 ° C to about 250 ° C, and a substrate coated with a cured thermosetting film is manufactured. The time can be changed according to the baking device and temperature used. For example, when a convection oven is used as a baking device, the time range may be from about 10 minutes to about 120 minutes. When using a hot plate, the time can vary from about 1 minute to about 60 minutes. In some embodiments, the temperature range may be from about 200 ° C to about 250 ° C. Those skilled in the art can routinely determine the appropriate time and temperature, which will depend on the specific solvents, thiols, end groups, additives and specific baking equipment used in the thermosetting composition.

In another embodiment, the temperature of the baking device can be increased. A suitable starting temperature range may be from about 80 ° C to about 180 ° C, and increased to a final temperature of from about 180 ° C to about 250 ° C, to manufacture a substrate coated with a cured thermosetting film. Those skilled in the art can routinely determine the appropriate starting and ending temperatures and the number of lifts. These will depend on the specific solvents, thiols, end groups, additives and use specifics used in the thermosetting composition bake Depending on the grilling device.

In another embodiment, the unbaked coated substrate can be baked in a two-step method. The unbaked coated substrate can be baked in a first baking step at a temperature between about 70 ° C and about 150 ° C for a period of time depending on the selected baking device, resulting in a dried and uncured Coated substrate. Preferably, the first baking temperature ranges from about 80 ° C to about 140 ° C (eg, from about 100 ° C to about 140 ° C or from about 100 ° C to about 130 ° C). The purpose of the first baking step is to evaporate the residual solvent from the film of the coated substrate predominantly without inducing the reverse addition ring-closing reaction. The first baking step can be used for a heating element on an inkjet print head.

Then, the dried uncured coated substrate can be baked in a second step at about 180 ° C to about 250 ° C, preferably at about 200 ° C to about 250 ° C, generating a cured heat Solid film coated substrate. Those skilled in the art can routinely determine the appropriate time and temperature, which will depend on the specific solvents, thiols, end groups, additives and specific baking equipment used in the composition.

The purpose of this second baking step is believed to be (1) causing the reverse addition ring-closing reaction on the polymer end groups to produce maleimide end groups, and (2) causing the maleimide on the polymer Crosslinking reaction between imine terminal groups and multifunctional thiol compounds.

The cross-linked polyimide film obtained from these method embodiments is an insulating film having excellent heat resistance, thermochemistry and electrical insulation properties.

In some embodiments, this disclosure feature is an object formed by the method described herein. Examples of such objects include a semiconductor substrate, A flexible film, a line of spacers, a line of coating, a wire coating, or an inked substrate for electronic products. In some embodiments, the feature of this disclosure is a semiconductor device containing the above object. For example, the semiconductor device may be an integrated circuit, a light-emitting diode, a solar cell, and a transistor.

In one embodiment, the present disclosure relates to a method for manufacturing a free-standing film of the thermosetting composition described herein. This method may include the following steps: a) coating a substrate with a thermosetting composition of the present disclosure to form a film-coated substrate, b) baking the film-coated substrate (for example, in a The first baking step, at a temperature T ₁ ), removes at least a portion (eg, substantially all) of the solvent in the thermosetting composition; and c) detaches the film coating from the substrate (eg, by applying A mechanical force or a chemical treatment) to obtain an independent membrane. In some embodiments, T ₁ may be less than about 150 ° C. Examples of suitable substrates that can be used in the above method include, without limitation, semiconductor materials such as silicon oxide wafers (which can promote the film detachment by using HF processing), and various plastic carriers such as polyterephthalic acid Ethylene glycol (PET) substrate (which is flexible and can be easily removed by peeling).

Optionally, additional processing of this film, such as exposure to radiation, corona, plasma and / or microwave radiation, or a second baking step at a temperature T ₂ (eg, from about 180 ° C to about 250 ° C) , Can be applied to cure the film coating after the first baking step and before the film becomes independent.

Alternatively, additional treatments that can be applied to the stand-alone membrane include, without limitation, washing the stand-alone membrane with water or solvent, and / or drying the stand-alone membrane.

Examples of mechanical force to remove this film include peeling without limitation. Examples of chemical treatments for detaching this membrane include, without limitation, treatment with dilute HF aqueous solution.

In some embodiments, once the independent film is formed, it can be applied to a semiconductor substrate suitable for semiconductor devices. Examples of such semiconductor substrates include printed circuit boards and flexible printed circuit boards.

The contents of all published materials cited herein (eg, patent cases, patent application publications, and articles) are hereby incorporated by reference for all.

The following examples are provided to more clearly illustrate the principles and implementation of the present invention. It should be understood that the invention is not limited to the examples described.

Synthesis Example 1 Synthesis of Polyimide PI-1

The polymerization reaction was carried out in a 1 liter three-necked round-bottom flask equipped with a mechanical stirrer, a thermocouple, and a nitrogen inlet that maintained a positive nitrogen pressure throughout the reaction. The flask was filled with 39.95 grams of 4,4 '-[1,4-phenylene-bis (1-methylethylene)] bisaniline (DAPI) and 600 grams of anhydrous NMP. The contents are stirred at 18-20 ° C until a homogeneous solution is obtained. Next, 61.08 grams of hexafluoroisopropylidene diphthalic anhydride (6-FDA) was injected into the stirred diamine solution through a funnel. The 6-FDA feed funnel was flushed into the reaction flask with 66.0 grams of anhydrous NMP. The mixture was warmed to 60 ° C and stirred for 3 hours.

In order to carry out the end cap reaction, 4.2 g other than -3,6-epoxy-1,2,3,6-tetra Hydrophthalic anhydride (oxonadi anhydride) and 2.0 grams of pyridine were injected into the flask. The mixture was stirred at 60 ° C for 3 hours.

To carry out the amide imidization reaction, 10.2 g of acetic anhydride and 2.0 g of pyridine were injected into the reaction vessel. The reaction mixture was warmed to 100 ° C and stirring continued for 12 hours. A small sample (1 g) was taken and precipitated in 50:50 methanol: water (10 mL). The solid was isolated by filtration and dried. FTIR analysis showed that the amidation reaction was complete.

The solution was cooled to room temperature and added dropwise to 4 liters of vigorously stirred deionized water to precipitate the polymer. The polymer was collected by filtration and washed with 1 liter of deionized water. The filter cake was slurried again with 1 liter of methanol and filtered. The wet filter cake was dried in the air for 12 hours, and then, the polymer was dried under vacuum at 70 ° C for 12 hours. The polymer was subjected to characterization analysis by GPC for molecular weight, ¹ H NMR for composition, FTIR for amide and anhydride-free peaks, Karl Fisher titration for water, and GC for residual solvent.

Synthesis Example 2 Synthesis of Polyimide PI-2

Using the procedure of Synthesis Example 1, except that the amount of reagents used is as follows: 39.95 grams of 4,4 '-[1,4-phenylene-bis (1-methylethylene)] bisaniline (DAPI), 300 grams of Anhydrous NMP, 61.08 grams of hexafluoroisopropylidene diphthalic anhydride (6-FDA), 33.0 grams of anhydrous NMP, 4.2 grams other than -3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 2.0 Grams of pyridine, 10.2 grams of acetic anhydride, and 2.0 grams of pyridine.

Synthesis Example 3-5 Synthesis of Polyimide PI-3, PI-4, and PI-5

Polyimides PI-3, PI-4, and PI-5 were synthesized according to the procedure of Synthesis Example 1, except for any changes shown in Table 1. The ODA in PI-5 is oxydiphenylamine.

Synthesis Example 6-12 and Comparative Synthesis Example 1 Synthesis of Polyimide Polymers PPI-6 to PPI-12 and (Comparative) Polyimide Polymer CPI-1

The polymer was prepared according to Synthesis Example 1 with the changes shown in Table 2. Table 3-5 contains the chemical structures of the reactants used in these examples.

Example of deployment FE-1 to FE-16

The thermosetting composition components described in the examples are mixed in an amber bottle, and a solvent mixture is added to adjust the solid content of the solution, and stirred until a uniform solution is obtained. This solution was filtered through a 1.0 μm filter into a clean amber bottle. Tables 6 and 7 contain the polythiol and adhesion listed in the formulations in Table 8 (Formulation Examples FE-1 to FE-16) and Table 11 (Formulation Examples FE17 to FE-23 and Comparative Formulation 1) Information on accelerators.

Example 1-9 Preparation of coated substrates with cured thermosetting coatings

A thermosetting composition prepared as above is spin-coated on a silicon wafer or a silicon dioxide wafer to form a coating having a thickness of from about 5 to about 30 microns. The coated wafers are baked at 120 ° C for 3 minutes. Coating defects and film cracks were examined by optical microscope. The film was heated in a convection oven at 200 ° C for 1 hour under N ₂ atmosphere. The formed film was inspected for film defects with an optical microscope. The membrane was immersed in various solvents (PGMEA, GBL, acetone and ether) to test the initial solvent resistance. When a silicon dioxide wafer is used as a substrate, the film is detached from the wafer by treatment with a 50: 1 water: HF solution. The detached film was dried in a drying cabinet under N ₂ for 24 hours. The dried film was used for mechanical testing (modulus, elongation at break, Tg and CTE) by TMA and DMA. Coating, baking, and other details are reported in Table 9, and mechanical properties are reported in Table 10. As shown in Table 9, the cured films of FE-6, FE-14, and FE-15 were insoluble in the test solvent.

SBFT = soft baked film thickness FT = film thickness INS = insoluble

Blending Examples FE-17 to FE-23 and Comparative Blending Example 1

Preparation Examples FE-17 to FE-23 and Comparative Preparation Example 1 were prepared according to the procedures described for Preparation Example 1 in the details shown in Table 11.

EL = ethyl lactate; PGME = propylene glycol monomethyl ether; CP = cyclopentanone; GBL = γ butyrolactone; CH = cyclohexanone MMB = 3-methyl-3-methoxybutanol; HP = 2- Heptanone; DMIS = 2,5-dimethylisosorbide DBU = diazabicycloundecene; DCMA = dicyclohexylamine; THA = trihexylamine

Example 10-16 and Comparative Example 1.

The formulations FE-17 to FE-23 were coated on silicon wafers and baked similarly to Examples 1-9, producing comparable results. CFE-1 was also coated and baked similarly, but when immersed in a solvent, it was completely removed from the wafer.

Ink-jet coated substrate with cured thermosetting coating

The thermosetting composition (2 ml) shown in Table 12 below is transferred via a syringe to an ink cartridge installed in a Dimatix DMP-2800 printer. The composition is divided between the piezoelectric frequency of 1-20KHz and the indicated temperature. As shown in Table 13, for Examples 17 and 18, the droplet size uniformity was found to be excellent, and the inkjet nozzles were not clogged when printing was resumed after 4, 24, and 72 hours after the operation was stopped. In contrast, Comparative Example 2 showed poor spraying at the beginning and after 4 and 24 hours, and no spraying after 72 hours of storage.

PAA-1 is a polyamic acid derived from the reaction of 4,4'-oxydiphenylamine (ODA) and 4,4'-oxydiphthalic anhydride (ODPA) in GBL at a ratio of 0.96: 1.00. The 18% by weight solution of this polymer has a dynamic viscosity in the range of 3000-5000 cSt.

Comparative Synthesis Example CSE-2 Synthesis of Polyimide CPI-2 (Comparative Example)

Polyimide CPI-2 was synthesized according to the procedure in Synthesis Example 1, except that the end cap group was replaced by 1,2,3,6-tetrahydro-3,6-methylenephthalic anhydride (Nadic anhydride) -3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (oxonadic acid anhydride). MW and PD are respectively 14, 116 Dalton and 4.0.

Comparative Synthesis Example CSE-3 Synthesis of Polyimide CPI-3 (Comparative Example)

Polyimide CPI-3 was synthesized according to the procedure in Synthesis Example 1, except that the dianhydride system was 4,4-oxodiphthalic anhydride (ODPA) and the diamine system was oxydiphenylamine (ODA). After the amide imidization step, a large amount of precipitate is obtained. This example shows that the typical polyimide has lower solubility in NMP than the polymer of the present disclosure.

Blending example FE-26, FE-27 and comparative example CFE-3

The thermosetting composition components described in Table 14 were mixed in an amber bottle, and a solvent mixture was added to adjust the solid content of the solution, and stirred until a uniform solution was obtained. This solution was filtered through a 1.0 μm filter into a clean amber bottle. Table 14 contains information about these formulations.

Example 19-21 Preparation of cured substrate with cured thermosetting coating from FE-26

The thermosetting composition FE-26 prepared above is spin-coated on a silicon wafer to form a coating having a thickness of from about 5 to about 15 microns. The coated wafers are baked at 120 ° C for 3 minutes. Coating defects and film rupture are examined by optical microscope. The film was heated in a convection oven at 200 ° C for 1 hour under N ₂ atmosphere. The formed film was inspected for film defects with an optical microscope. This membrane is immersed in various solvents (PGMEA, GBL, acetone, and others) to test the initial solvent resistance. The results of these tests are shown in Table 15.

INS = Insoluble

Example 22-24 Preparation of coated substrate with cured thermosetting coating from FE-27

These experiments were performed exactly as in Examples 19-21, except that the thermosetting composition of FE-27 was used, and the film was heated in a convection oven at 250 ° C instead of 200 ° C for 1 hour under N ₂ atmosphere. The results of these tests are shown in Table 16.

INS = Insoluble

Comparative examples CE-3 to CE-5 Preparation of coated substrates with cured thermosetting coatings from CFE-3

These experiments were performed exactly as described in Example 19-21, except that the composition of CFE-3 was used. The results of these tests are shown in Table 17.

PI-1 (ST-1 to ST-5) and CPI-3 (CST-1 to CST-5) solubility test

9 grams of solvent (listed in Table 18) and 1 gram of polymer PI-1 or The comparative polymer CPI-3 was added to a vial. Then, each vial was stirred on a roller to help dissolve the polymer.

The vial containing polymer PI-1 was completely dissolved in all tested solvents within 30 minutes. An additional 0.25 g of increasing amount of polymer PI-1 was added repeatedly to small, and rolled again for 30 minutes until the last part was added. The final rolling period was extended from 30 minutes to overnight. Table 18 contains information on the amount of solvent-soluble polymer PI-1 (ST-1 to ST-5).

The comparative polymer CPI-3 is insoluble in all solvents in an amount of 10% (9 grams of solvent to 1 gram of polymer). 10 grams of additional solvent was added to each of the 5 vials containing comparative polymer CPI-3, and the vial was rolled overnight. After rolling overnight, a large portion of the comparative polymer CPI-3 remained undissolved, indicating <5% solubility in the solvent (see Table 18, CST-1 to CST-5).

This experiment shows that the polymer of the present disclosure has a greater solubility advantage than typical polyimide.

Claims (24)

A polymer, comprising: a first repeating unit, the first repeating unit comprising at least one amide imine portion and at least one indane-containing portion; and at least one end capping group which is attached to one end of the polymer , The end cap group contains a masked maleimide group; wherein, the end cap group contains a structure (IXa) part:

Among them, G series -O-,-(NR ¹⁰⁰ )-,-[C (R ¹⁰¹ ) = C (R ¹⁰² )]-, or-[C = C (R ¹⁰³ ) ₂ ]-, where, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , and R ^{103 are} each independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic or polycyclic alkyl group, or a substituted Or unsubstituted phenyl group, and each of R ¹ , R ² , R ³ and R ⁴ is independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic Or polycyclic alkyl group, a substituted or unsubstituted phenyl group, OR ¹⁰⁴ , CH ₂ OR ¹⁰⁵ , CH ₂ OC (= O) R ¹⁰⁶ , CH ₂ C (= O) OR ¹⁰⁷ , CH ₂ NHR ¹⁰⁸ , CH ₂ NHC (= O) R ¹⁰⁹ , CH ₂ C (= O) N (R ¹¹⁰ ) ₂ , C (= O) OR ¹¹¹ , where R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , and R ^{111 are} each independently H, or a substituted or unsubstituted C ₁ -C ₆ linear, branched, or monocyclic alkyl group. The polymer according to claim 1, wherein the end cap group can undergo a reverse addition ring-closing reaction. The polymer according to claim 1, wherein the indane-containing portion contains

Wherein, each of R ¹¹ -R ³⁰ is independently H or a substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl group. The polymer of claim 3, wherein each of R ¹¹ -R ³⁰ is independently H or CH ₃ . The polymer according to claim 1, further comprising a second repeating unit different from the first repeating unit. The polymer of claim 1, wherein the polymer has structure I:

Among them, Z is a divalent organic group capable of undergoing anti-addition ring-bonding reaction, n is an integer greater than 5, each X is independently a divalent organic group, and each Y is independently a tetravalent organic group Group, and at least one of X and Y includes an indane-containing portion. The polymer of claim 1, wherein the polymer has a weight average molecular weight of at least 1,000 grams / mole. A polymer comprising the following condensation products: (a) at least one diamine; (b) at least one dianhydride; and (c) at least one monoanhydride, which is a masked maleic anhydride group; wherein, the components at least one of (a) and (b) includes an indane-containing portion, the polymer includes at least one end capping group at one end, the end capping group includes a masked maleic anhydride group, and the The masked maleic anhydride structure (IX):

Among them, G series -O-,-(NR ¹⁰⁰ )-,-[C (R ¹⁰¹ ) = C (R ¹⁰² )]-, or-[C = C (R ¹⁰³ ) ₂ ]-, where, R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , and R ^{103 are} each independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic or polycyclic alkyl group, or a substituted or Unsubstituted phenyl group, and each of R ¹ , R ² , R ³ and R ⁴ is independently H, a substituted or unsubstituted C ₁ -C ₁₂ linear, branched, monocyclic or Polycyclic alkyl group, a substituted or unsubstituted phenyl group, OR ¹⁰⁴ , CH ₂ OR ¹⁰⁵ , CH ₂ OC (= O) R ¹⁰⁶ , CH ₂ C (= O) OR ¹⁰⁷ , CH ₂ NHR ¹⁰⁸ , CH ₂ NHC (= O) R ¹⁰⁹ , CH ₂ C (= O) N (R ¹¹⁰ ) ₂ , C (= O) OR ¹¹¹ , where R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , Each of R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , and R ¹¹¹ is independently H or a substituted or unsubstituted C ₁ -C ₆ linear, branched, or monocyclic alkyl group. The polymer according to claim 8, wherein the end cap group can undergo a reverse addition ring-closing reaction. The polymer according to claim 8, wherein the indane-containing portion contains

Wherein, each of R ¹¹ -R ³⁰ is independently H or a substituted or unsubstituted C ₁ -C ₁₀ linear or branched alkyl group. The polymer of claim 10, wherein each of R ¹¹ -R ³⁰ is independently H or CH ₃ . The polymer of claim 8, wherein the component comprising the indane-containing portion is at least about 25 mole% of components (a) and (b). A thermosetting composition comprising: the polymer of claim 1; at least one multifunctional thiol compound, the thiol compound comprising at least two thiol groups; at least one solvent; and optionally at least one non-nucleophilic Basic additives. The composition of claim 13, wherein the multifunctional thiol compound has the structure (VI):

Where a is an integer ranging from 2 to 10; c is an integer ranging from 1 to 10; each of b, d, and e is independently an integer ranging from 0 to 1; f, g, and h Each is independently an integer ranging from 0 to 10; Q is a multivalent organic core; each of Z ¹ , W, and Z ¹¹ is independently a bivalent linking group; R ⁷¹ and R ⁷² Each is independently H, a substituted or unsubstituted linear or branched C ₁ -C ₆ alkyl group, or a substituted or unsubstituted C ₃ -C ₁₀ cycloaliphatic group; and M It is a substituted or unsubstituted C ₁ -C ₆ linear or branched aliphatic group, a substituted or unsubstituted C ₃ -C ₁₀ cycloaliphatic group, or a substituted or unsubstituted C ₆ -C ₁₈ mononuclear or polynuclear aromatic group. The composition of claim 13, further comprising at least one non-nucleophilic basic additive. The composition of claim 15, wherein the non-nucleophilic basic additive is a nitrogen-containing compound or a phosphorus-containing compound. The composition of claim 13, wherein the polymer is from about 1% to about 50% by weight of the composition. The composition of claim 13, wherein the multifunctional thiol compound is from about 0.2% to about 30% by weight of the composition. The composition of claim 13, wherein the solvent is at least about 40% by weight of the composition. A method for manufacturing a thermosetting coating, comprising: coating a substrate with the thermosetting composition of claim 13 to form a coated substrate, and baking the coated substrate to cure the thermosetting composition In order to form a thermosetting coating on the substrate. The method of claim 20, wherein coating the substrate comprises coating the thermosetting composition by inkjet printing, spin coating, spray coating, dip coating, roller coating, or dynamic surface tension coating On the substrate. A method for manufacturing a self-supporting film, comprising: coating a substrate with the thermosetting composition of claim 13 to form a film-coated substrate, and baking the film-coated substrate to remove at least a portion Part of the at least one solvent, and the film coating is separated from the substrate to obtain a self-supporting film. A self-supporting film obtained by the manufacturing method of claim 22. A device comprising a coated substrate prepared by the manufacturing method of claim 20.